Arylation of Axially Chiral Phosphorothioate Salts by Dinuclear PdI Catalysis. (9th July 2019)

• Record Type: Journal Article
• Authors: Chen, Xiang‐Yu; Pu, Maoping; Cheng, Hong‐Gang; Sperger, Theresa; Schoenebeck, Franziska
• Is Part Of: Angewandte Chemie. Volume 131:Number 33(2019)
• Page Start: 11517
• Page End: 11521
• Publication Date: 2019-07-09
• Subjects: Arylierungen -- Axiale Chiralität -- Computerchemie -- Dinukleare Katalyse -- S-Arylphosphorothioat; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201906063
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: S‐aryl phosphorothioates are privileged motifs in pharmaceuticals, agrochemicals, and catalysts; yet, the challenge of devising a straightforward synthetic route to enantioenriched S‐aryl phosphorothioates has remained unsolved to date. We demonstrate herein the first direct C−SP(=O)(OR′)(OR′′) coupling of diverse and chiral phosphorothioate salts with aryl iodides, enabled by an air‐ and moisture‐stable Pd I dimer. Our mechanistic and computational data suggest distinct dinuclear Pd I catalysis to be operative, which allows for operationally simple couplings with broad scope and full retention of stereochemistry. Abstract : Die erste direkte C‐SP(=O)(OR′)(OR′′)‐Kupplung unterschiedlicher und chiraler Phosphorothioatsalze mit Aryliodiden gelang mithilfe eines luft‐ und feuchtigkeitsstabilen Pd I ‐Dimers. Mechanistische und Computer‐Daten sprechen für eine spezifische dinukleare Pd I ‐Katalyse, die operativ einfache Kupplungen mit einer großen Substratbandbreite bei vollständiger Retention der Konfiguration ermöglicht.